Photographic coating compositions

ABSTRACT

A PHOTOGRAPHIC COATING AID HAVING THE FORMULA   R-O-CH2-CH(-O-A)-CH2-SO2-O-M OR   R-O-CH2-CH(-O-A)-CH2-N(-B)-CH2-CH2-SO2-O-M   WHEREIN R IS A HYDROCARBON RADICAL HAVING 4-18 CARBON ATOMS OR A PHENYL GROUP HAVING A C4-18 HYDROCARBON RADICAL. A IS HYDROGEN OR ALOWER ACYL GROUP, B IS HYDROGEN OR METHYL AND M IS A CATION, IS INCORPORATED INTO A PHTOTGRAPHIC COATING COMPOSITION IN AN AMOUNT OF 0.01 TO 20 G/KG. OF COMPOSITION.

United States Patent 3,824,102 PHOTOGRAPHIC COATING COMPOSITIONS Masao Ishihara and Sllui Sato, Tokyo, Eiichi Sakamoto, Hanno, and Osakazu Sugino, Tokyo, Japan, assignors to Konishiroku Photo Industry Co., Ltd., Tokyo, Japan No Drawing. Continuation of application Ser. No. 757,505, Sept. 4, 1968. This application Oct. 13, 1971, Ser. No. 189,036

Int. Cl. B01f 17/00; G03c 1/28, 1/40 US. Cl. 96-100 8 Claims ABSTRACT OF THE DISCLOSURE a photographic coating composition in an amount of 0.01 to 20 g./kg. of composition.

This application is a Rule 60 continuation of copending parent application Ser. No. 757,505 filed Sept. 4, 1968. The priority of Japanese applications 58,329/ 1967 filed Sept. 13, 1967, and 58,639/ 1967 filed Sept. 14, 1967, respectively, is claimed.

This invention relates to a photographic coating composition which comprises as a coating aid a surface active agent of the general formula in which R is a hydrocarbon radical having 4-18 carbon atoms or a phenyl group containing a C hydrocarbon radical, A is hydrogen or a lower acyl group, B is hydrogen or methyl group and M is a cation e.g. Na, K, NH etc. Formation of uniform photographic coatings is an object of the invention.

Photographic light-sensitive materials usually comprise a support such as glass plate, baryta paper, nitrocellulose, acetylcellulose, polycarbonate, etc. and a plurality of layers coated thereon. Among these layers are included subbing layer, light-sensitive emulsion layer, protective layer, filter layer, anti-halation layer, etc. In the routine work of the art, these layers are formed on the film support by applying a coating liquid (solution, emulsion or dispersion) to the support by means of the dipping process, double roller method, slide hopper method and then drying the coating. In this case, it is very essential to apply a variety of coating liquids onto the entire surface of the support at a uniform thickness. In the prior art, however, unevenness arising in the coating direction (referred to as longitudinal unevenness or transverse unevenness) and local imperfection of coating (referred to as comets) or unevenness at the peripheral zone are occasionally observed. In order to prevent such drawice backs, use of a coating aid, e.g. a surface tension depressant for coating liquids, is well known in the art.

Among the known coating aids, saponin is the most common. Because saponin is a material of the natural origin, however, it is unavoidable that the quality is not settled and different from each batch'. Even if the same quality of saponin were used, significant varieties in photographic characteristics and properties as coating aids can be observed.

In place of saponin, use of various synthetic surface active agents has been proposed. However, among known surface active agents, only a very few of them are satisfactory, as they exert an adverse effect on the photographic characteristics, especially degradation of storability at high temperature under high humidity and the coating efiiciency thereof in high speed coating is insufiicient.

According to this invention, a compound of the aforementioned general formula is incorporated into various photographic coating liquids as a coating aid. Such compound has good surface activity and does not cause any adverse effect on photographic emulsion. Moreover, no variety in quality as observed in the use of saponin is brought about and a small amount of such compound is effective to decrease surface tension of a coating liquid and to reduce contact angle. Viscosity is not increased even by the use of the above compound. Therefore, not only the coating at an ordinary speed but also high speed coating at about 40 m./min. as well as double-layer coating are facilitated without formation of any unevenness and comets to form very uniform coating.

Compared with saponin, the compound No. 2 or No. 19 referred to hereinafter as a compound covered by the afore-mentioned general formula shows the following surface tension and contact angle on being used as the coating liquid:

Measurement of the surface tension was made by means of Du Nauy method by adding the indicated amount of 3%-aqueous solution of the compound No. 2 or No. 19 to the high speed emulsion containing 10% gelatine. The contact angle to the triacetyl cellulose film base subjected to the subbing treatment by means of the alkali saponification (Treatment A) or the subbing treatment with vinyl maleic acid resin (Treatment B) was measured. The results thus obtained are shown in the table below along with the results obtained by using saponin in the similar way. As the control, the emulsion containing no additive was used.

Surface Contact angle (40 C.)

It is apparent from the above table that the surface tension and contact angle are reduced by the compounds used in this invention and rather superior results are obtained by using saponin which has therefore been used conveniently. Thus, according to the invention, uniform coating is available and any adverse effect is not caused on photographic characterics as observed in the case of known synthetic surface active agents being used.

3 Typical compounds which are usable in the present invention will be illustrated below. However, it should be noted that they are merely illustrative of compounds embraced by the general formula and that the scope of the invention is not limited thereto.

Syntheses of the above compounds are disclosed in Journal of the Chemical Society of Japan (Industrial Chemistry Section), vol. 63, page 595 (1960) and vol. 66, page 215 (1963) and in U.S. Pats. 2,989,547 and 3,084,187.

Such compounds are added to photographic coating liquid as a solution dissolved in water or a water-miscible organic solvent, such as methanol, ethanol, acetone, etc. These compounds are usually satisfactory as a coating aid in an amount of 001-20 g. per 1 kg. of various photographic coating liquids. Such amount of the above compounds are used as a dispersion or solution of 1-10% concentration. Such compounds may be employed in combination with other surface active agent.

Incorporation of the above compounds into a lightsensitive photographic emulsion can be made at any stage during the ripening. In general, said compounds are added to the photographic emulsion after the ripening and just before coating. The light-sensitive photographic emulsion used in this invention may be chemically sensitized by way of gold-, sulfuror polyalkylene oxide-sensitization or optically sensitized by a light-sensitive dye. The emulsion may contain an azaindene stabilizer or a hardener. An emulsion for color film containing a color former may also be useable.

The following examples illustrate the present invention.

EXAMPLE 1 A high speed silver iodobromide emulsion subjected to the secondary ripening was added with an adequate amount of a stabilizer. To each of the emulsion was added the compounds according to this invention as indicated below, or, as control, saponin or a heretofore known synthetic surfactant, p-tert.octylphenyl polyethylene glycol ether sulfonic acid ester sodium salt of the formula rmmQ-owmomoms OzNa (Control A) Such emulsions were then coated on subbed (by the alkali saponification) surface of triacetyl cellulose film base by means of the dipping process. Uniformity of coatings and photographic properties of the resulted films were examined. The results thus obtained are shown in Table 1.

TABLE 1 Photographic characteristics Ineubated at Immediately Incubated at 50 C. and 80% after the 55 C. for 3 RH. for 3 preparation days after the days after the of emulsion preparation preparation Amount added Relative Relative Relative Compound added (percent) Coating property speed Fog speed Fog speed Fog None Unevenness and repellency observed 100 0.03 101 0.04 100 0.03

on all of the surface. saponin 0.06 }Un iform coating available without 100 0.03 102 0.06 101 0.05 either unevenness or repelleney. 102 0.04 103 0.06 102 0.05 100 0.03 101 0.05 98 0.04 0.12 i' f 101 0.03 102 0.00 00 0.04 Compound number:

0.06} 100 0.03 100 0.04 102 0.04 0.12 102 0.03 102 0.04 101 0.03 0.00 100 0.03 100 0.03 101 0.03 0.12 100 0.04 101 0.04 100 0.04 0.06 101 0.03 100 0.04 101 0.03 0.12 100 0.04 101 0.05 100 0.04 0.06} 101 0.03 102 0.03 102 0.04 0.12 100 0.04 100 0.05 101 0.04 0.0e} do 100 0.03 100 0.04 101 0.03 0.12 102 0.04 101 0.04 100 0.04 0.06 100 0.03 100 0.03 101 0.03 0.12 102 0.03 103 0.04 100 0.03

As apparent from the above Table 1, uniform coatings or were always available according to the present invention without any fear of local incomplete coating and uneven 1'3 coailng- H RO-CH CHCH NCH-CH,S03M

In addltlon that such uniform coating 1s avallable, any I A adverse effect is caused on photographic characteristics. Photographic characteristics were stably maintained even under severe lncubat n C01 d 0 wherein R is a hydrocarbon radical having 4-8 carbon EXAMPLE 2 atoms or a phenyl group having a C hydrocarbon radical, A is hydrogen or a lower acyl group, B is hydrogen or methyl and M is a cation.

2. The photographic coating composition as claimed in Claim 1, wherein said compound is used in combination with a surface active agent.

3. The photographic coating composition as claimed in claim 1, wherein said composition comprises gelatin, said coating aid compound being represented by the formula TAB LE 2 Photographic Amount added (percent) characteristics Emulsion Protective Relative Compound added layer layer Coating property speed Fog Saponin 0. 12 0. 06 Uniform coating available without 100 0. 03

either unevenness or repelleney. Compound number:

What is claimed is:

1. A photographic coating composition comprising 0.01- 20 g. per kg. of coating composition of a coating aid compound having the formula R-o-cm-on-orh-s OaM wherein R is a hydrocarbon radical having 4-18 carbon atoms or a phenyl group having a C hydrocarbon radical, A is hydrogen or a lower acyl group and M is a cation.

4. The photographic coating composition as claimed in claim 1, wherein said composition comprises gelatin,

7 said coating aid compound being represented by the formula R-o-cm-c H--C H,NC H,O H,-s 03M wherein R is a hydrocarbon radical having 4-18 carbon atoms or a phenyl group having a C hydrocarbon radical, A is hydrogen or a lower acyl group, B is hydrogen or a methyl and M is a cation.

5. A composition according to claim 1 wherein said composition is a light-sensitive photographic silver halide emulsion.

6. The emulsion as claimed in Claim 5, further containing an optical sensitizer.

7. The emulsion as claimed in Claim 5, further containing a color former.

8. The emulsion as claimed in Claim 5, further containing a sulfur-, gold-, reductive or polyalkylene oxide RONALD H. SMITH, Primary Examiner A. T. SURO PICO, Assistant Examiner US. Cl. X.R. 

